Aliphatic tertiary amines are important industrial intermediates for preparing corrosion inhibitors, fungicides, dye adjuvants and softening agents for fabrics, etc. and there are a number of methods known for their preparation.
N,N-dimethylalkylamides can be reduced commercially to tertiary amines at high temperature and pressure in the presence of Cu--Cr catalysts. See S. H. Shapiro in E. S. Pattison, ed., Fatty Acids and Their Industrial Applications, Marcel Dekker, Inc. New York, 1968, p. 124.
The catalytic amination of aliphatic alcohols is likely the most economic and simplest route to tertiary amines. In a recent article by Abe et al. in Applied Catalysis, 52, 171 (1989) is described the production of N,N-dimethyldodecylamine from dodecyl alcohol and dimethylamine using copper stearate and nickel stearate, although the likely active catalysts are colloidal copper and nickel. This article also reviews earlier catalyst studies on this route to aliphatic tertiary amines, including the use of Cu--Re, Raney nickel and supported Cu--Sn--Na catalysts.
A catalyst of Cu--Cr--Ba has been used in alkylation of long-chain amines with short-chain alcohols to yield tertiary amines. See Brit. Pat. 675,852 (Jan. 16, 1957) (to Armour & Co.) and Jpn. Kokai 74 82,605 (Aug. 8, 1974) and 74 81,306 (Aug. 6, 1974).
U.S. Pat. No. 3,223,734 teaches the alkylation of long-chain amines to high molecular weight tertiary amines by treating the amine with a long-chain alcohol in the presence of Raney nickel or Cu--Cr catalyst.
A method has been disclosed for producing tertiary amines wherein a dodecyl alcohol and dimethyl amine are reacted in the presence of a suspended copper chromium catalyst. See 19 Japan Patent Agency (JP) 12 Kokai Patent Gazette (A), 11 Publication No: 59-222 448 [84-222448] 43 Publication Date: Dec. 14, 1984.
In an article titled "Recent Trends of Catalysts for Production of Aliphatic Tertiary Amines", Okabe Kazuhiko and Abe Hiroshi (Wakayama First Res. Lab., Kao Corp. Wakayama, Japan) Yukagaku, 1988, 37(7), 485-91 (Japan), there is a review of catalysts which are suitable for amination of alkanols, with the authors having researched and developed the performance of copper-nickel amination catalysts in particular.
Tallow alcohol has been reacted with dimethylamine vapor over a catalyst comprising copper carbonate and nickel carbonate to produce dimethylalkylamine. See U.S. Pat. No. 4,683,336.
In Soap/Cosmetics/Chemical Specialties, Febuary 1985, p. 54, there is discussed a technological breakthrough in amine chemical manufacture by Onyx Chemical Company wherein detergent range fatty alcohols are catalytically reacted directly with diethylamine, by-passing the traditional hydrochlorination step, thus allowing for a cleaner, easier to control tertiary amine with very precise alkyl radical distribution.
European Patent Application No. 0 239 934 demonstrates the selective production of mono-aminated products from the amination of ethylene glycol or 1,3-propanediol with a secondary amine which is effected in the presence of a ruthenium compound.
In PCT Int. Appl. WO 88 06,579 (C1. CO7C93/04), Sep. 7, 1988, there is disclosed the amination of alkoxylated alcohols with secondary amines in the presence of a catalyst comprising a mixture of CuO or Cu(OH).sub.2.
Other art involving the preparation of tertiary amines describes catalysts containing copper, alkaline earth metals, copper chromite, Cu--Ni--Ru, Cu--Sn, Cu--Cr, Cu--Zn/Al.sub.2 O.sub.3, Pd--C and Pt group metals. Generally the reactants include alcohols and primary or secondary amines.
See for example:
U.S. Pat. No. 3,128,311 PA1 U.S. Pat. No. 4,625,063 PA1 U.S. Pat. No. 4,625,064 PA1 E.P. 233,317 PA1 Ger. Offen. DE 3,246,978 PA1 Ger. Offen. DE 3,523,074 PA1 Ger. Offen. DE 3,432,015-A PA1 J. P. 59,106,441 PA1 J. P. 59,222,448 PA1 J. P. 62,149,646 PA1 J. P. 62,149,647 PA1 CN 85,100,326
The principal uses of dialkylamines and trialkylamines are discussed in an article titled "Cationic Surfactants", Stanford Research Institute, December (1985), p. 8. The majority of the dialkylamines produced via fatty nitrile chemistry are subsequently converted to quaternary ammonium salts.
From a survey of the available art it appears the source of the alcohol reacted with an amine is often from naturally-occurring raw materials such as coconut oil, tallow and tall oil.
There is a comparison of the cost of production of C.sub.12 dimethyl fatty amines by the synthetic petrochemical route using, for example, Ziegler alcohols, compared with similar tertiary nitrogen chemicals derived from naturally occurring raw materials such as coconut oil, tallow or tall oil in Chem Systems, Process Evaluation/Research Planning, Report No. 85-6 (September '86) at Sec. 1.3000.
For the most part, the art referred to focuses on the synthesis of N,N-dimethylalkylamines by reaction of dimethylamine or monomethylamine with a long chain alcohol, e.g. tallow alcohol or dodecyl alcohol. It would be an important advance in the art to have a process for the selective production of "twin tailed" N-methyldialkylamines, particularly "twin-tailed" N-methyldi(polyoxyalkylene)tertiary amines, that could be produced from readily available reactants in yields which are improvements over yields for related tertiary amines.